The rational modification of electronic structures to create catalytically active sites has been proved to be a promising strategy to efficiently facilitate the urea oxidation reaction (UOR). Herein, a well-defined nanosheet arrays catalyst of Ni(OH)2 doped with dual cations of Co and Mn on Ni foam (NF) (Co/Mn-Ni(OH)2) is synthesized through a simple hydrothermal process. Benefiting from the advantages of unique structures and modified binding strengths, it is found experimentally that the obtained Co/Mn-Ni(OH)2 catalyst only requires a potential of 1.38 V to deliver a current density of 100 mA cm-2 and exhibits a small Tafel slope of 35 mV dec-1, outperforming single-component-incorporated Ni(OH)2. Moreover, the catalyst has shown excellent stability for 25 h at a current density of 50 mA cm-2. Additionally, first-principles calculations demonstrate that the co-incorporation of Co and Mn remarkably lowers the adsorption barrier of CO(NH2)2* on the catalyst surface, and accelerates the dissociation of the CO(NH2)2* intermediate into CO* and NH* intermediates, which synergistically improve the UOR reaction kinetics. This work provides a generic paradigm for designing advanced and effective catalysts toward the UOR.